CN113372577A - Modified biochar composite hydrogel, and preparation method and application thereof - Google Patents
Modified biochar composite hydrogel, and preparation method and application thereof Download PDFInfo
- Publication number
- CN113372577A CN113372577A CN202110608634.5A CN202110608634A CN113372577A CN 113372577 A CN113372577 A CN 113372577A CN 202110608634 A CN202110608634 A CN 202110608634A CN 113372577 A CN113372577 A CN 113372577A
- Authority
- CN
- China
- Prior art keywords
- aqueous solution
- composite hydrogel
- polyvinyl alcohol
- modified biochar
- acrylic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000017 hydrogel Substances 0.000 title claims abstract description 81
- 239000002131 composite material Substances 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 70
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 70
- 235000002637 Nicotiana tabacum Nutrition 0.000 claims abstract description 65
- 241000208125 Nicotiana Species 0.000 claims abstract description 64
- 239000007864 aqueous solution Substances 0.000 claims abstract description 56
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 45
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000002689 soil Substances 0.000 claims abstract description 41
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 24
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims abstract description 17
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 58
- 239000000243 solution Substances 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 claims description 11
- 238000005303 weighing Methods 0.000 claims description 11
- 235000017060 Arachis glabrata Nutrition 0.000 claims description 10
- 244000105624 Arachis hypogaea Species 0.000 claims description 10
- 235000010777 Arachis hypogaea Nutrition 0.000 claims description 10
- 235000018262 Arachis monticola Nutrition 0.000 claims description 10
- 235000020232 peanut Nutrition 0.000 claims description 10
- 239000012153 distilled water Substances 0.000 claims description 8
- 230000007935 neutral effect Effects 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 239000007800 oxidant agent Substances 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 3
- 239000003610 charcoal Substances 0.000 claims 1
- 238000012986 modification Methods 0.000 claims 1
- 230000004048 modification Effects 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 24
- 238000001179 sorption measurement Methods 0.000 abstract description 20
- 229910052793 cadmium Inorganic materials 0.000 abstract description 10
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 abstract description 10
- 231100000331 toxic Toxicity 0.000 abstract description 6
- 230000002588 toxic effect Effects 0.000 abstract description 6
- 238000011161 development Methods 0.000 abstract description 4
- 230000003647 oxidation Effects 0.000 abstract description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 2
- 238000004132 cross linking Methods 0.000 abstract 1
- 239000003431 cross linking reagent Substances 0.000 abstract 1
- 238000007865 diluting Methods 0.000 abstract 1
- 239000003999 initiator Substances 0.000 abstract 1
- 230000003472 neutralizing effect Effects 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 25
- 238000012360 testing method Methods 0.000 description 19
- 238000011282 treatment Methods 0.000 description 18
- 238000010521 absorption reaction Methods 0.000 description 11
- 102000016938 Catalase Human genes 0.000 description 7
- 108010053835 Catalase Proteins 0.000 description 7
- 102000003992 Peroxidases Human genes 0.000 description 7
- 102000019197 Superoxide Dismutase Human genes 0.000 description 7
- 108010012715 Superoxide dismutase Proteins 0.000 description 7
- 108040007629 peroxidase activity proteins Proteins 0.000 description 7
- 229910001385 heavy metal Inorganic materials 0.000 description 6
- 239000000499 gel Substances 0.000 description 5
- 230000008961 swelling Effects 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 238000009616 inductively coupled plasma Methods 0.000 description 4
- 239000002028 Biomass Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- 229930002875 chlorophyll Natural products 0.000 description 2
- 235000019804 chlorophyll Nutrition 0.000 description 2
- ATNHDLDRLWWWCB-AENOIHSZSA-M chlorophyll a Chemical compound C1([C@@H](C(=O)OC)C(=O)C2=C3C)=C2N2C3=CC(C(CC)=C3C)=[N+]4C3=CC3=C(C=C)C(C)=C5N3[Mg-2]42[N+]2=C1[C@@H](CCC(=O)OC\C=C(/C)CCC[C@H](C)CCC[C@H](C)CCCC(C)C)[C@H](C)C2=C5 ATNHDLDRLWWWCB-AENOIHSZSA-M 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000029087 digestion Effects 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 244000061176 Nicotiana tabacum Species 0.000 description 1
- 241001002356 Valeriana edulis Species 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 description 1
- 208000005882 cadmium poisoning Diseases 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000001684 chronic effect Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000012844 infrared spectroscopy analysis Methods 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 210000000496 pancreas Anatomy 0.000 description 1
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000004382 potting Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000010496 root system development Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 210000000952 spleen Anatomy 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 238000002054 transplantation Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/261—Synthetic macromolecular compounds obtained by reactions only involving carbon to carbon unsaturated bonds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28047—Gels
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Dispersion Chemistry (AREA)
- Analytical Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention belongs to the technical field of composite hydrogel materials, and particularly relates to a modified biochar composite hydrogel, a preparation method and application thereof. The composite hydrogel is prepared by taking biochar, polyvinyl alcohol and acrylic acid as starting raw materials, modifying the biochar by nitric acid to obtain modified biochar, heating and dissolving the polyvinyl alcohol to obtain a polyvinyl alcohol aqueous solution, diluting the acrylic acid, neutralizing by potassium hydroxide to obtain a neutralized acrylic acid aqueous solution, adding initiator ammonium persulfate and cross-linking agent N, N' -methylene bisacrylamide into the measured modified biochar, polyvinyl alcohol aqueous solution and neutralized acrylic acid aqueous solution, and heating for cross-linking polymerization reaction. The composite hydrogel has strong Cd adsorption capacity, can adsorb cadmium in soil in tobacco planting, relieves the toxic action of tobacco seedlings under Cd stress, improves the SPAD value of the tobacco seedlings, enhances the oxidation resistance and stress resistance of the tobacco seedlings, and promotes the growth and development of the tobacco seedlings.
Description
Technical Field
The invention belongs to the technical field of composite hydrogel materials, and particularly relates to a modified biochar composite hydrogel, a preparation method and application thereof in tobacco planting.
Background
Cadmium is an unnecessary element for human bodies, exists in a compound state in the nature, has low content under normal conditions, and cannot influence the health of the human bodies. However, when the environment is polluted by cadmium, the cadmium can be gathered in water and soil, enter the human body through the enrichment of food chains, and gather in organs of the human body, such as liver, kidney, spleen, pancreas and the like, so that chronic cadmium poisoning of the human body is caused, and the health of the human body is damaged.
In order to minimize the cadmium entering the human body through the enrichment of the food chain, measures are taken to reduce the cadmium content in water or soil. The hydrogel as a composite material can be used for adsorbing cadmium ions in wastewater due to a certain adsorption effect. At present, scholars prepare hydrogel and use the hydrogel for adsorbing cadmium ions in waste water or soil, wherein an invention patent with the publication number of CN11211040A discloses that composite hydrogel is prepared by adopting peanut shell biochar, the hydrogel can adsorb the cadmium ions in the soil, the toxic action of the cadmium ions on tobacco seedlings is reduced, and a new direction of the composite hydrogel in tobacco planting is created. However, researches show that the composite hydrogel can achieve the purpose of adsorbing the content of cadmium ions in soil and has a certain adsorption effect on cadmium, but the adsorption effect is still not ideal to a certain extent.
Disclosure of Invention
Aiming at the problem that the adsorption effect of the existing biochar composite hydrogel on cadmium ions is not ideal, the invention provides the modified biochar composite hydrogel which can greatly improve the adsorption effect on the cadmium ions, reduce the toxic action of cadmium on tobacco seedlings to a greater extent and promote the growth of the tobacco seedlings.
The technical scheme adopted by the invention for solving the technical problems is as follows: the peanut shell biochar composite hydrogel comprises modified biochar, a 5% polyvinyl alcohol aqueous solution, a neutralized acrylic acid aqueous solution, ammonium persulfate and N, N' -methylene bisacrylamide, wherein the modified biochar is as follows: aqueous polyvinyl alcohol solution: and the mass of the ammonium persulfate is 0.05-0.07% of the mass sum of the polyvinyl alcohol aqueous solution and the neutralized acrylic acid aqueous solution, and the mass of the N, N' -methylene-bis-acrylamide is 0.03-0.05% of the mass sum of the polyvinyl alcohol aqueous solution and the neutralized acrylic acid aqueous solution.
The modified biochar composite hydrogel is prepared by the following steps: 5% aqueous polyvinyl alcohol solution: the mass of the ammonium persulfate is 0.06 percent of the mass sum of the polyvinyl alcohol aqueous solution and the neutralized acrylic acid aqueous solution, and the mass of the N, N' -methylene bisacrylamide is 0.04 percent of the mass sum of the polyvinyl alcohol aqueous solution and the neutralized acrylic acid aqueous solution.
The invention also provides a preparation method of the modified biochar composite hydrogel, which comprises the following steps
Firstly, putting peanut shell biochar into 12 mol.L-1Heating and stirring the nitric acid solution at 50-70 ℃, reacting for 5-7h, and repeatedly washing the nitric acid solution to be neutral by using distilled water so as to remove redundant oxidant and water-soluble compound; then, drying the sample in an oven at 110 ℃ to obtain modified biochar, grinding the modified biochar, and sealing and storing the biochar by a sieve with the diameter of 0.15mm for later use;
secondly, adding polyvinyl alcohol into deionized water, and dissolving the polyvinyl alcohol in water bath at 90-100 ℃ to obtain 5% polyvinyl alcohol aqueous solution;
thirdly, mixing acrylic acid and deionized water according to the volume ratio of 1: 5 carry outMixing, using 5 mol. L-1Neutralizing with potassium hydroxide to pH 7-8 to obtain neutralized acrylic acid aqueous solution;
fourthly, weighing the modified biochar, 5 percent polyvinyl alcohol solution and neutralized acrylic acid aqueous solution according to the proportion, adding ammonium persulfate and N, N' -methylene bisacrylamide, placing the beaker into a temperature-controllable water bath magnetic stirrer after uniformly stirring, adding a rotor, and stirring at the temperature of 60-70 ℃ for 350 r.min at 250--1Reacting for 5-7h at the rotating speed to obtain the modified biochar composite hydrogel.
The preparation method of the modified biochar composite hydrogel comprises the step of adding 12 mol.L of peanut shell biochar-1Heating and stirring the mixture in a nitric acid solution at 60 ℃, reacting for 6 hours, and repeatedly washing the mixture with distilled water to be neutral.
In the preparation method of the modified biochar composite hydrogel, in the second step, polyvinyl alcohol is added into deionized water and dissolved under heating in a water bath at 95 ℃.
The preparation method of the modified biochar composite hydrogel comprises the third step of using 5 mol. L-1The potassium hydroxide is neutralized to pH 7.5 to obtain a neutralized acrylic acid aqueous solution.
The fourth step of the preparation method of the modified biochar composite hydrogel is at 300 r.min under the temperature condition of 65 DEG C-1Reacting for 6 hours at the rotating speed to obtain the modified biochar composite hydrogel.
The modified biochar composite hydrogel disclosed by the invention is applied to tobacco planting.
The modified biochar composite hydrogel is applied to tobacco planting, and plays a role in water retention in tobacco planting.
The modified biochar composite hydrogel can adsorb cadmium ions in soil in tobacco planting and promote tobacco growth.
The invention has the beneficial effects that:
(1) the modified biochar composite hydrogel has good water absorption and retention performance, and the swelling degree can reach 101.69 g.g-1Can effectively keep the water content in the soil,the water loss speed of the soil is reduced.
(2) The modified biochar composite hydrogel disclosed by the invention can adsorb Cd in an aqueous solution2+The maximum adsorption capacity can reach 259.57mg g-1Has extremely high adsorption effect and can effectively reduce the toxic action of cadmium on tobacco seedlings.
(3) The composite hydrogel provided by the invention can be used for treating Cd in soil2+Has strong adsorption and fixation capacity, and can effectively reduce the content of effective Cd in soil.
(4) The modified biochar composite hydrogel disclosed by the invention can promote the growth of tobacco seedling leaves and roots, increase the number of the tobacco seedling leaves, improve the phenotype of tobacco leaves, promote the development of the roots and improve the biomass and relative water content of tobacco.
(5) The modified biochar composite hydrogel disclosed by the invention can improve the SPAD value (P is less than 0.05) of tobacco seedlings under Cd stress, and effectively relieves the toxic action of Cd on the tobacco seedlings.
(6) The tobacco seedling treated by the modified biochar composite hydrogel provided by the invention has the advantages that the peroxidase POD activity, the catalase CAT activity and the superoxide dismutase SOD activity are obviously improved, the oxidation resistance of the tobacco seedling is enhanced, and the stress resistance is improved.
(7) The modified biochar composite hydrogel can obviously reduce the effective Cd content in soil and the Cd accumulation amount in tobacco seedling leaves, and is beneficial to the growth of tobacco.
Drawings
FIG. 1 is an FTIR spectrum of a composite hydrogel of the present invention.
FIG. 2 is an SEM image of the composite hydrogel of the present invention.
FIG. 3 is a diagram showing the state of the composite hydrogel of the present invention before and after water absorption.
FIG. 4 shows the results of the change in water content of the soil before and after the use of the composite hydrogel of the present invention.
FIG. 5 shows the results of the change in soil quality before and after the use of the composite hydrogel of the present invention.
FIG. 6 shows the effect of the composite hydrogel material on the growth of tobacco leaves under Cd stress.
FIG. 7 shows the results of the effect of different treatments on the SPAD value of tobacco.
FIG. 8 shows the effect of different treatments on the POD, SOD and CAT content of tobacco.
FIG. 9 is a graph of the effect of different treatments on the available Cd content of soil.
FIG. 10 is a graph of the effect of different treatments on the Cd content of tobacco lamina.
FIG. 11 is a diagram showing the morphology of the composite hydrogel after gelling.
Detailed Description
The invention is further illustrated with reference to the following figures and examples.
Example 1: the modified biochar composite hydrogel provided by the embodiment comprises nitric acid modified biochar, a 5% polyvinyl alcohol aqueous solution, a neutralized acrylic acid aqueous solution, ammonium persulfate and N, N' -methylene bisacrylamide, wherein the ratio of the modified biochar: 5% aqueous polyvinyl alcohol solution: the mass of ammonium persulfate is 0.06% of the mass sum of the polyvinyl alcohol aqueous solution and the neutralized acrylic acid aqueous solution, and the mass of N, N' -methylene bisacrylamide is 0.04% of the mass sum of the polyvinyl alcohol aqueous solution and the neutralized acrylic acid aqueous solution.
The preparation method comprises the following steps:
firstly, putting peanut shell biochar into 12 mol.L-1Heating and stirring at 60 ℃ in the nitric acid solution, reacting for 6 hours by using peanut shell biochar provided by Henan Huiyong soil conservation research and development Limited company, and repeatedly washing with distilled water to be neutral to remove redundant oxidant and water-soluble compound; then, drying the sample in an oven at 110 ℃ to obtain modified biochar, grinding the modified biochar, and sealing and storing the biochar by a sieve with the diameter of 0.15mm for later use;
secondly, adding 1g of polyvinyl alcohol into 20mL of deionized water, and dissolving in a water bath at 95 ℃ to obtain a 5% polyvinyl alcohol aqueous solution;
thirdly, 9mL of acrylic acid is added into 45mL of deionized water, and 5 mol.L of acrylic acid is used-1Neutralizing with potassium hydroxide to pH 7.5 to obtain neutralized acrylic acid aqueous solution;
fourthly, weighing 1g of modified biochar, adding the 5 percent polyvinyl alcohol solution and the neutralized acrylic acid solution, and adding 0.06g of sulfurous acidAmmonium sulfate and 0.06g of N, N' -methylene bisacrylamide are evenly stirred, the beaker is placed in a temperature-controllable water bath magnetic stirrer, a rotor is added, and 300 r.min is carried out at the temperature of 65 DEG C-1Reacting for 6 hours at the rotating speed to obtain the modified biochar composite hydrogel.
Example 2: the modified biochar composite hydrogel provided by the embodiment comprises nitric acid modified biochar, a 5% polyvinyl alcohol aqueous solution, a neutralized acrylic acid aqueous solution, ammonium persulfate and N, N' -methylene bisacrylamide, wherein the ratio of the modified biochar: aqueous polyvinyl alcohol solution: the mass of the ammonium persulfate is 0.06% of the mass sum of the polyvinyl alcohol aqueous solution and the neutralized acrylic acid aqueous solution, and the mass of the N, N' -methylene bisacrylamide is 0.04% of the mass sum of the polyvinyl alcohol aqueous solution and the neutralized acrylic acid aqueous solution.
The preparation method comprises the following steps:
firstly, putting peanut shell biochar into 12 mol.L-1The nitric acid solution is heated and stirred at 60 ℃, reacted for 6 hours, and repeatedly washed by distilled water to be neutral so as to remove redundant oxidant and water-soluble compounds. Then, drying the sample in an oven at 110 ℃ to obtain modified biochar, grinding the modified biochar, and sealing and storing the biochar by a sieve with the diameter of 0.15mm for later use;
secondly, adding 1g of polyvinyl alcohol into 20mL of deionized water, and dissolving in a water bath at 95 ℃ to obtain a 5% polyvinyl alcohol aqueous solution;
thirdly, 9mL of acrylic acid is added into 45mL of deionized water, and 5 mol.L of acrylic acid is used-1Neutralizing with potassium hydroxide to pH 7.5 to obtain neutralized acrylic acid aqueous solution;
fourthly, weighing 0.5g of modified biochar, adding the 5 percent polyvinyl alcohol solution and the neutralized acrylic acid solution, adding 0.06g of ammonium persulfate and 0.06g of N, N' -methylene bisacrylamide, stirring uniformly, placing the beaker in a temperature-controllable water bath magnetic stirrer, adding a rotor, and stirring at 65 ℃ for 300 r.min-1Reacting for 6 hours at the rotating speed to obtain the modified biochar composite hydrogel.
Example 3: the modified biochar composite hydrogel provided by the embodiment comprises nitric acid modified biochar, a 5% polyvinyl alcohol aqueous solution, a neutralized acrylic acid aqueous solution, ammonium persulfate and N, N' -methylene bisacrylamide, wherein the ratio of the modified biochar: aqueous polyvinyl alcohol solution: the mass of the ammonium persulfate is 0.06% of the mass sum of the polyvinyl alcohol aqueous solution and the neutralized acrylic acid aqueous solution, and the mass of the N, N' -methylene bisacrylamide is 0.04% of the mass sum of the polyvinyl alcohol aqueous solution and the neutralized acrylic acid aqueous solution.
The preparation method comprises the following steps:
firstly, putting peanut shell biochar into 12 mol.L-1The nitric acid solution is heated and stirred at 60 ℃, reacted for 6 hours, and repeatedly washed by distilled water to be neutral so as to remove redundant oxidant and water-soluble compounds. Then, drying the sample in an oven at 110 ℃ to obtain modified biochar, grinding the modified biochar, and sealing and storing the biochar by a sieve with the diameter of 0.15mm for later use;
secondly, adding 1g of polyvinyl alcohol into 20mL of deionized water, and dissolving in a water bath at 95 ℃ to obtain a 5% polyvinyl alcohol aqueous solution;
thirdly, 9mL of acrylic acid is added into 45mL of deionized water, and 5 mol.L of acrylic acid is used-1Neutralizing with potassium hydroxide to pH 7.5 to obtain neutralized acrylic acid aqueous solution;
fourthly, weighing 1.5g of modified biochar, adding the 5 percent polyvinyl alcohol solution and the neutralized acrylic acid solution, adding 0.06g of ammonium persulfate and 0.04g of N, N' -methylene bisacrylamide, stirring uniformly, placing the beaker in a temperature-controllable water bath magnetic stirrer, adding a rotor, and stirring at 65 ℃ for 300 r.min-1Reacting for 6 hours at the rotating speed to obtain the modified biochar composite hydrogel.
Test example 1: structural characterization
(1) Infrared spectroscopic analysis
The modified biochar composite hydrogel prepared in the example 1 iS dried and then used as a material sample to be uniformly mixed with potassium bromide powder for tabletting, the mixture iS placed on an iS10 type infrared spectrometer for scanning, and the scanning wave number range iS 4000-500cm-1The results are shown in FIG. 1, in which PVA/AA (a) is polyvinyl alcohol/acrylic acid hydrogel, PVA/AA/MB (b) is polyvinyl alcohol/acrylic acid/modified biochar hydrogel000～500cm-1FT-IR plot over the range, PVA/AA with similar peak shapes to PVA/AA/MB. FIG. 1, Curve b, shows the characteristic functional groups of PVA/AA at 3419cm-1The characteristic peak of the position is attributed to O-H stretching vibration. -COOH and-COO-The groups are respectively 1717, 1542 and 1403cm-1Characteristic stretching vibration bands appear. It can be seen that the PVA/AA/B and PVA/AA/MB are at 3419cm-1The peak shape of the PVA/AA/MB is changed, and the peak shape intensity of the PVA/AA/MB is enhanced and is 1717, 1542 and 1403cm-1The peak shape of the gel also changes to different degrees, which indicates that the novel biochar hydrogel is formed.
(2) Scanning electron microscope
The composite hydrogel prepared in example 1 was freeze-dried, then subjected to gold spraying, and placed on a SIGMA-500 scanning electron microscope for microscopic observation, and the results are shown in FIG. 2.
As can be seen from FIG. 2, the PVA/AA/MB has larger and denser pores, and the macroporous network structure increases the effective contact area of the hydrogel and heavy metal ions, thereby being beneficial to the adsorption of the hydrogel on the heavy metal ions.
Test example 2: water absorption and retention effect
(1) Water absorption test
Weighing 0.30g of dried composite hydrogel material, soaking in distilled water for 48h to reach swelling balance, taking out hydrogel, wiping surface water with filter paper, weighing, and obtaining the formula SR ═ We-W0)/W0Testing the water absorption performance of the water absorption material, wherein: SR is swelling degree (g.g)-1)；W0A xerogel mass (g); weThe gel mass (g) at swelling equilibrium and the water absorption results are shown in FIG. 3.
FIG. 3 is a photograph of the composite hydrogel material of the present invention before and after water absorption, and it can be seen from the gel state before and after water absorption that the composite hydrogel prepared by the present invention has good water absorption performance, and the swelling degree calculated by the formula is 101.69g g.g-1。
(2) Water retention test
Weighing 1g of dried composite hydrogel material with phi of 0.25mm, uniformly mixing the hydrogel material with air-dried fine soil, taking the hydrogel material without water as a blank control CK, adding water in a consistent amount, and adding water at room temperatureStanding for 7 days, weighing every 2 days, and using formula W ═ Me-M0)/M0Calculating the water content of the soil in different time periods to verify the water retention effect, wherein W is the water content (%) of the soil; meThe soil mass (g) after water absorption balance, M0The results of the change in the water content of the soil before and after use and the results of the change in the soil quality are shown in FIGS. 4 and 5, which show the dry soil quality (g).
As can be seen from FIGS. 4 and 5, the water content of the soil added with the composite hydrogel material PVA/AA/MB is obviously higher than that of the blank soil after being placed for different times, which indicates that the composite hydrogel material has stronger water retention performance, can effectively keep the water in the soil and reduce the water loss speed.
Test example 3: cd adsorption test
0.05g of the dried composite hydrogel material having a diameter of 0.25mm was fully immersed in 100mL of analytically pure cadmium nitrate (Cd (NO)3)2) Prepared Cd with concentration of 150mg/L2+In the solution, oscillating on an oscillator for 24h to achieve adsorption balance, and measuring Cd in the adsorbed solution by adopting an ICP-OES inductively coupled plasma atomic emission spectrometer2+The concentration of (C) is represented by the formula Q ═ Ce-C0)·V]Calculating the adsorption capacity of the composite material to the heavy metal Cd, wherein Q is the adsorption capacity (mg. g) of the composite hydrogel material to the heavy metal Cd-1)；C0Is Cd2+Initial concentration of (mg. L)-1)；CeFor adsorption of Cd in equilibrium2+Concentration of (mg. L)-1) (ii) a m is the mass (g) of the xerogel.
ICP detection shows that Cd in the solution after adsorption balance2+Has a concentration of 20.22 mg.L-1And the composite hydrogel material PVA/AA/MB can be obtained by calculation for Cd2+Has an adsorption amount of 259.57mg g-1。
Test example 4: tobacco pot growth test
Adding 55 mg/kg-1(quality of Cd: quality of dried soil) potting test is carried out under the condition of Cd, 200g of dried soil sieved by 0.425mm phi is added into each pot, a water-free gel material is used as a blank control CK, an experimental group B T1 is added, and PVA/AA is added as a trueTest group T2, adding MB to test group T3, adding PVA/AA/MB to test group T4, and adding PVA/AA/B to test group T5. Before transplanting, dry soil and dry gel are uniformly mixed at a ratio of 1.5:1000, tobacco seedlings with the same growth vigor of 30 days are selected for transplanting, 10 plants are treated each time, and the influence of the composite material on the growth and development of the tobacco seedlings under the Cd stress is researched. The tobacco seedlings were photographed 20 days after transplantation, and the growth thereof was observed, with the results shown in fig. 6;
and (3) scanning the tobacco root system by using a Japanese EPSON V800 root system scanner, and analyzing the tobacco seedling root system by using a root system analysis system WinRHIO. The total root length, total root surface area, average root diameter, number of root tips and root volume of tobacco seedlings were measured, and the results are shown in table 1.
TABLE 1 results of various indexes of different groups of tobacco seedlings
As can be seen from Table 1, the addition of the composite hydrogel material promotes the growth of tobacco seedlings, enhances the promotion of root system development, and significantly increases the total root length, the total root surface area, the average root diameter, the number of root tips and the root volume under the stress of Cd, which indicates that the composite hydrogel provided by the invention can effectively relieve the toxic effect of Cd on the tobacco seedlings, improve the phenotype of the tobacco seedlings and promote the growth and development of the root systems.
Test example 5: tobacco biomass assay
The method for measuring the biomass of the tobacco comprises the following steps: sampling the overground part and the underground part of the tobacco plant, weighing by using an analytical balance, and recording the fresh weight of the sample.
The above-ground part and the underground part of the fresh tobacco are subjected to enzyme deactivation in an oven at 105 ℃ for 30min, then dried to constant weight at 65 ℃, weighed by an analytical balance, and the dry weight of the sample is recorded. The results are shown in Table 2.
As can be seen from Table 2, the treatment with the added material significantly increased both the fresh weight and the dry weight of tobacco under Cd stress compared to the control (P <0.05), with the greatest improvement in T4 treatment, the fresh weight increased by 231.48% and the dry weight increased by 188.24% for T4 treatment compared to the control.
TABLE 2 fresh and Dry weights of tobacco seedlings of different groups
Test example 6: tobacco seedling SPAD value determination
Selecting the third tobacco leaf subjected to Cd treatment for 20 days as a material. The SPAD value of tobacco was measured using a portable chlorophyll apparatus of Japan Konica Minolta SPAD 502 PLUS.
It can be seen from fig. 7 that the SPAD value of the T4 treatment is significantly higher (P <0.05) than the other treatments. The SPAD values of other treatments except T2 are obviously improved compared with CK (P is less than 0.05), and the influence of Cd stress on chlorophyll of tobacco seedlings is obviously improved.
Cd stress alone resulted in a significant decrease in SPAD index and photosynthesis index, which was alleviated by the application of PVA/AA/MB.
Test example 7: influence of POD, SOD and CAT content in tobacco
Taking the 3 rd true leaf of each treatment as a material. The activities of Peroxidase (POD), superoxide dismutase (SOD) and Catalase (CAT) were tested using a specific test kit (Beijing Solarbio, Beijing, China) according to the manufacturer's instructions.
From fig. 8, it can be seen that the treatment treatments other than T1 (P <0.05) significantly increased the SOD activity of tobacco seedlings compared to CK, and each treatment significantly (P <0.05) increased the POD activity and the CAT activity of tobacco seedlings, with the treatment at T4 being most significant. POD activity, SOD activity and CAT activity of T4-treated tobacco seedlings are respectively improved by 97.99%, 268.66% and 167.76% (P < 0.05). The PVA/AA/MB can improve the activity of the antioxidant enzyme of the tobacco leaves under the stress of Cd and improve the stress resistance of tobacco seedlings.
Test example 8: influence of effective Cd content in soil
And (3) determining the effective Cd in the soil: the air-dried soil was extracted with CaCl2-DTPA-TEA and then measured by inductively coupled plasma emission spectrometry (ICP-OES).
FIG. 9 shows that the effective Cd content of each treated soil is significant (P) when the adsorbing material is added<0.05) less than or equal toCompared with CK treatment by adding an adsorption material, the content of effective Cd in soil treated by adding T4 has significant difference, and the content of the effective Cd in the soil treated by adding T4 is reduced most obviously relative to CK. The content of effective Cd in the soil treated by T4 is reduced by 65.18%. Cd in soil by PVA/AA/MB2+Has strong adsorption and fixation capacity.
Test example 9: effect of tobacco leaf Cd content
And (3) determining the content of Cd in the tobacco leaves: weighing the enzyme-deactivating sample, putting the enzyme-deactivating sample into a full-automatic digestion instrument for digestion, and measuring the digested solution by using an inductively coupled plasma emission spectrometer (ICP-OES).
As shown in FIG. 10, the Cd contents of the treated tobacco leaves added with the adsorbing materials are all obvious (P)<0.05) is lower than CK treatment, the content of Cd in the tobacco leaves treated by T4 is reduced most obviously compared with CK, and the content of Cd in the tobacco leaves is reduced by 63.23 percent, which is consistent with the trend of reducing the effective cadmium in soil. Each treated material can adsorb heavy metal Cd in the polluted soil2+Thereby reducing the heavy metal Cd in the soil2+The effectiveness of the method is shown in the specification, wherein T4 is the most obvious, which indicates that PVA/AA/MB has stronger Cd adsorption and fixation2+The ability of the cell to perform.
Claims (9)
1. A modified biochar composite hydrogel is characterized in that: the modified biochar comprises modified biochar, a 5% polyvinyl alcohol aqueous solution, a neutralized acrylic acid aqueous solution, ammonium persulfate and N, N' -methylene bisacrylamide, wherein the modified biochar is as follows: aqueous polyvinyl alcohol solution: and the mass of the ammonium persulfate is 0.05-0.07 percent of the mass sum of the polyvinyl alcohol aqueous solution and the acrylic acid aqueous solution, and the mass of the N, N' -methylene-bis-acrylamide is 0.03-0.05 percent of the mass sum of the polyvinyl alcohol aqueous solution and the acrylic acid aqueous solution.
2. The modified biochar composite hydrogel of claim 1, wherein: modified charcoal: 5% aqueous polyvinyl alcohol solution: the mass of the ammonium persulfate is 0.06% of the mass sum of the polyvinyl alcohol aqueous solution and the acrylic acid aqueous solution, and the mass of the N, N' -methylene-bis-acrylamide is 0.04% of the mass sum of the polyvinyl alcohol aqueous solution and the acrylic acid aqueous solution.
3. A method for preparing the modified biochar composite hydrogel according to any one of claims 1 or 2, which is characterized in that: comprises the following steps
Firstly, putting peanut shell biochar into 12 mol.L-1Heating and stirring the nitric acid solution at 50-70 ℃, reacting for 5-7h, and repeatedly washing the nitric acid solution to be neutral by using distilled water so as to remove redundant oxidant and water-soluble compound; then, drying the sample in an oven at 110 ℃ to obtain modified biochar, grinding and passing through a 0.15mm sieve for sealing and storing for later use;
secondly, adding polyvinyl alcohol into deionized water, and dissolving the polyvinyl alcohol in water bath at 90-100 ℃ to obtain 5% polyvinyl alcohol aqueous solution;
thirdly, mixing acrylic acid and deionized water according to the volume ratio of 1: 5, mixing with 5 mol. L-1Neutralizing with potassium hydroxide to pH 7-8 to obtain neutralized acrylic acid aqueous solution;
fourthly, weighing the modified biochar, 5 percent polyvinyl alcohol solution and neutralized acrylic acid solution according to the proportion, adding ammonium persulfate and N, N' -methylene bisacrylamide, placing the beaker into a temperature-controllable water bath magnetic stirrer after uniformly stirring, adding a rotor, and stirring at the temperature of 60-70 ℃ for 350 r.min at 250--1Reacting for 5-7h at the rotating speed to obtain the modified biochar composite hydrogel.
4. The preparation method of the modified biochar composite hydrogel according to claim 3, which is characterized in that: in the first step, the peanut shell biochar is put into 12 mol.L-1Heating and stirring the nitric acid solution at 60 ℃, reacting for 6 hours, and repeatedly washing the nitric acid solution to be neutral by using distilled water.
5. The preparation method of the modified biochar composite hydrogel according to claim 3, which is characterized in that: in the second step, polyvinyl alcohol is added into deionized water and dissolved in water bath at 95 ℃ under heating.
6. Modification according to claim 3The preparation method of the biochar composite hydrogel is characterized by comprising the following steps: in the third step, 5 mol. L is used-1The potassium hydroxide is neutralized to pH 7.5 to obtain a neutralized acrylic acid aqueous solution.
7. The preparation method of the modified biochar composite hydrogel according to claim 3, which is characterized in that: in the fourth step, the temperature is controlled at 65 ℃ and the temperature is controlled at 300 r.min-1Reacting for 6 hours at the rotating speed to obtain the modified biochar composite hydrogel.
8. Use of the modified biochar composite hydrogel of claim 1 or 2 in tobacco planting.
9. The application of the modified biochar composite hydrogel in tobacco planting according to claim 8 is characterized in that: the modified biochar composite hydrogel can adsorb and fix cadmium ions in soil in tobacco planting, and tobacco growth is promoted.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110608634.5A CN113372577B (en) | 2021-06-01 | 2021-06-01 | Modified biochar composite hydrogel, preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110608634.5A CN113372577B (en) | 2021-06-01 | 2021-06-01 | Modified biochar composite hydrogel, preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113372577A true CN113372577A (en) | 2021-09-10 |
| CN113372577B CN113372577B (en) | 2024-01-26 |
Family
ID=77575244
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110608634.5A Active CN113372577B (en) | 2021-06-01 | 2021-06-01 | Modified biochar composite hydrogel, preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113372577B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114643049A (en) * | 2022-05-24 | 2022-06-21 | 山东石油化工学院 | Preparation method of organic chelating agent doped biochar composite hydrogel |
| CN114752023A (en) * | 2022-03-30 | 2022-07-15 | 河南农业大学 | Preparation and application of degradable molecular sieve composite hydrogel |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102633949A (en) * | 2012-05-16 | 2012-08-15 | 苏州宜生生物技术有限公司 | Method for preparing semi-interpenetrating network hydrogel |
| CN104707566A (en) * | 2015-02-17 | 2015-06-17 | 中国海洋大学 | Charcoal sphere as well as preparation method and application thereof |
| CN106633111A (en) * | 2017-01-11 | 2017-05-10 | 福州大学 | Method for preparing high-strength polyvinyl alcohol-based dual-network hydrogel |
| CN106750380A (en) * | 2016-11-28 | 2017-05-31 | 吉林大学珠海学院 | A kind of polymer-modified environmentally friendly composite aquogel and its application in heavy metal containing sewage is processed |
| CN107115843A (en) * | 2017-05-23 | 2017-09-01 | 江苏大学 | A kind of preparation method and applications for coming from peanut shell modified activated carbon |
| CN107903406A (en) * | 2017-09-14 | 2018-04-13 | 刘志勇 | A kind of preparation method of three network aqueous gel of high intensity selfreparing |
| CN108342041A (en) * | 2018-02-08 | 2018-07-31 | 燕山大学 | A kind of preparation method of the double ion collaboration crosslinking antibacterial hydrogel of rapidly self-healing type |
| CN109334173A (en) * | 2018-10-17 | 2019-02-15 | 燕山大学 | A kind of water-keeping gel material and preparation method thereof |
| CN109749752A (en) * | 2019-01-12 | 2019-05-14 | 吴义峰 | A kind of preparation method of sand fixation material |
| US20190358365A1 (en) * | 2015-12-04 | 2019-11-28 | Poly-Med, Inc. | Double network hydrogel with anionic polymer and uses therof |
| CN111875915A (en) * | 2020-08-10 | 2020-11-03 | 李娟� | High-strength SiO2-polyacrylic acid-polyvinyl alcohol interpenetrating network hydrogel and preparation method thereof |
| CN112111040A (en) * | 2020-09-12 | 2020-12-22 | 河南农业大学 | Peanut shell biochar composite hydrogel and application thereof in tobacco planting |
-
2021
- 2021-06-01 CN CN202110608634.5A patent/CN113372577B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102633949A (en) * | 2012-05-16 | 2012-08-15 | 苏州宜生生物技术有限公司 | Method for preparing semi-interpenetrating network hydrogel |
| CN104707566A (en) * | 2015-02-17 | 2015-06-17 | 中国海洋大学 | Charcoal sphere as well as preparation method and application thereof |
| US20190358365A1 (en) * | 2015-12-04 | 2019-11-28 | Poly-Med, Inc. | Double network hydrogel with anionic polymer and uses therof |
| CN106750380A (en) * | 2016-11-28 | 2017-05-31 | 吉林大学珠海学院 | A kind of polymer-modified environmentally friendly composite aquogel and its application in heavy metal containing sewage is processed |
| CN106633111A (en) * | 2017-01-11 | 2017-05-10 | 福州大学 | Method for preparing high-strength polyvinyl alcohol-based dual-network hydrogel |
| CN107115843A (en) * | 2017-05-23 | 2017-09-01 | 江苏大学 | A kind of preparation method and applications for coming from peanut shell modified activated carbon |
| CN107903406A (en) * | 2017-09-14 | 2018-04-13 | 刘志勇 | A kind of preparation method of three network aqueous gel of high intensity selfreparing |
| CN108342041A (en) * | 2018-02-08 | 2018-07-31 | 燕山大学 | A kind of preparation method of the double ion collaboration crosslinking antibacterial hydrogel of rapidly self-healing type |
| CN109334173A (en) * | 2018-10-17 | 2019-02-15 | 燕山大学 | A kind of water-keeping gel material and preparation method thereof |
| CN109749752A (en) * | 2019-01-12 | 2019-05-14 | 吴义峰 | A kind of preparation method of sand fixation material |
| CN111875915A (en) * | 2020-08-10 | 2020-11-03 | 李娟� | High-strength SiO2-polyacrylic acid-polyvinyl alcohol interpenetrating network hydrogel and preparation method thereof |
| CN112111040A (en) * | 2020-09-12 | 2020-12-22 | 河南农业大学 | Peanut shell biochar composite hydrogel and application thereof in tobacco planting |
Non-Patent Citations (1)
| Title |
|---|
| 涂征 等: ""聚丙烯酸钠/聚乙烯醇复合水凝胶的制备及其电响应行为"", 《中国塑料》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114752023A (en) * | 2022-03-30 | 2022-07-15 | 河南农业大学 | Preparation and application of degradable molecular sieve composite hydrogel |
| CN114752023B (en) * | 2022-03-30 | 2023-03-10 | 河南农业大学 | Preparation and application of degradable molecular sieve composite hydrogel |
| CN114643049A (en) * | 2022-05-24 | 2022-06-21 | 山东石油化工学院 | Preparation method of organic chelating agent doped biochar composite hydrogel |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113372577B (en) | 2024-01-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112111040B (en) | Peanut shell biochar composite hydrogel and application thereof in tobacco planting | |
| CN113372577B (en) | Modified biochar composite hydrogel, preparation method and application thereof | |
| Pehlivan et al. | Modified barley straw as a potential biosorbent for removal of copper ions from aqueous solution | |
| CN110681350A (en) | Preparation method of phosphoric acid modified enteromorpha biological carbon and application of phosphoric acid modified enteromorpha biological carbon in removal of heavy metal cadmium | |
| CN109529773A (en) | Iris is enriched with the preparation method and applications of the charcoal of manganese element | |
| CN106179202A (en) | A kind of composite modified biological carbon materials of iron-based amino and preparation and application | |
| CN109908867A (en) | A method of strengthening removal water body ammonia nitrogen with sulfonation charcoal | |
| CN105435748A (en) | Plant cellulose adsorbent | |
| CN114456809A (en) | Magnesium modified bamboo dust charcoal and application thereof in soil carbon sequestration and emission reduction | |
| CN111101216B (en) | Polyacrylonitrile-hydroxyurea chelate fiber and synthetic method and application thereof | |
| CN110122271A (en) | A kind of straw biological charcoal base vegetables basin alms bowl cultivation matrix and its system | |
| Katircioğlu et al. | Chromium (VI) biosorption from aqueous solutions by free and immobilized biomass of Oscillatoria sp. H1 isolated from freshwater | |
| CN102631889B (en) | Eichhornia crassipes adsorbing material and preparation method thereof | |
| Cohen-Shoel et al. | The involvement of pectin in Sr 2+ biosorption by Azolla | |
| CN114752023B (en) | Preparation and application of degradable molecular sieve composite hydrogel | |
| CN110484269A (en) | A kind of heavy-metal contaminated soil renovation agent and its preparation and application method | |
| JP2017178723A (en) | Manufacturing method of active charcoal | |
| CN111659348B (en) | Manganese-loaded plant-based biochar and preparation method and application thereof | |
| CN112403444B (en) | Modified biochar for reducing methyl mercury enrichment in rice and method | |
| CN113245357B (en) | Method for adsorbing heavy metals in soil by using propiconazole and geomembrane source micro-plastic | |
| CN109777429B (en) | Humic acid source soil heavy metal effective state regulating agent and application thereof | |
| RU2564337C1 (en) | Silica gel-based sorption material with immobilised thiosemicarbazide | |
| CN111303894A (en) | Lignin-based composite stabilizer for in-situ remediation of heavy metal pollution in soil and preparation method thereof | |
| CN109701502A (en) | Novel chelate fibre and preparation method thereof and in lime-preserved egg Pb (II) detection application | |
| CN104058801B (en) | A kind of preparation method of ammino acid liquid fertilizer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |